EP2220129A2 - Activation de supports basés sur des complexes de phosphonium - Google Patents

Activation de supports basés sur des complexes de phosphonium

Info

Publication number
EP2220129A2
EP2220129A2 EP08860188A EP08860188A EP2220129A2 EP 2220129 A2 EP2220129 A2 EP 2220129A2 EP 08860188 A EP08860188 A EP 08860188A EP 08860188 A EP08860188 A EP 08860188A EP 2220129 A2 EP2220129 A2 EP 2220129A2
Authority
EP
European Patent Office
Prior art keywords
activating
support
silica
ethylene
phosphonium
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP08860188A
Other languages
German (de)
English (en)
Inventor
Abdelkrim El Kadib
Karine Molvinger
Daniel Brunel
Floran Prades
Sabine Sirol
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
TotalEnergies One Tech Belgium SA
Centre National de la Recherche Scientifique CNRS
Original Assignee
Total Petrochemicals Research Feluy SA
Centre National de la Recherche Scientifique CNRS
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Total Petrochemicals Research Feluy SA, Centre National de la Recherche Scientifique CNRS filed Critical Total Petrochemicals Research Feluy SA
Priority to EP08860188A priority Critical patent/EP2220129A2/fr
Publication of EP2220129A2 publication Critical patent/EP2220129A2/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/50—Organo-phosphines
    • C07F9/5022—Aromatic phosphines (P-C aromatic linkage)
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F110/02—Ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/65912—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an organoaluminium compound
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/6592—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring

Definitions

  • the present invention discloses the preparation of solid activating systems for the polymerisation of olefins.
  • the present invention relates to an activating support for immobilising metallocene or post-metallocene complexes, in order to promote heterogeneous polymerisation of ethylene and alpha-olefins .
  • catalysts are however not adapted to heterogeneous polymerisation, such as suspension or gas phase polymerisation. These processes offer many advantages, among others, they allow the preparation of a polymer in granular form having a defined particles size distribution.
  • That activating agent however also exhibits disadvantageous features such as superstoechiometric quantities of MAO ranging from MAO:catalyst precursor ratios of 10 2 :1 to 10 4 :1. Consequently, there is a great need to develop new activating agents that can either replace MAO or decrease its necessary quantities.
  • borane-based organic Lewis acid as alternative to MAO to activate metallocenes as polymerisation catalysts in homogeneous conditions has been extensively studied by several groups, (see for example: E. Y.-X. Chen, T.J. Marks, "Cocatalysts for metal-catalyzed polymerization: Activators, Activation processes, and structure-activity relationships" in Chem. Rev., 100, 1391-1434, 2000).
  • the activating agent was a perfluoroborate that comprised a non coordinating anion with a low charge of -1 or -2, that easily achieves charge delocalisation and that is capable of providing single cation active species to a catalyst precursor.
  • the cationic moiety of the activating agent reacts with a leaving group of a metal precursor to provide a cationic active site such as for example (Cp 2 alkylmetal) + in the case of metallocene.
  • a metal precursor such as for example (Cp 2 alkylmetal) + in the case of metallocene.
  • the latter forms an ion pair with the anionic part of cocatalyst system.
  • the anion weakly coordinates to the metal and is easily exchanged with an olefin monomer, resulting in polymerisation.
  • these "ion-pair" activating systems suffer from low thermal and chemical stability and are very sensitive to solvents and monomers. The design of stable and robust systems is thus very desirable.
  • a neutral amine compound is produced during catalyst activation: it can interact strongly with a cationic catalyst, thereby poisoning active sites and competing with olefin monomer coordination. Hence, the polymerisation activity was drastically reduced. To avoid this problem, ammonium cation can be replaced by phosphonium.
  • Another goal of this invention is the preparation of heterogeneous olefin polymerisation catalytic systems having hardened catalyst grains for use in gas phase or slurry polymerisation processes and then to provide a method for preparing polymers having improved morphology, thereby reducing reactor fouling such as described for example in Fink et al. (G. Fink, B. Steinmetz, J. Zechlin, C. Przybyla, B. Tesche, "Propene polymerization with silica-supported metallocene/MAO catalysts", in Chem. Rev., 100, 1377- 90, 2000).
  • Heterogenisation can optionnaly be performed by covalent anchorage of the metallocene complexes on mineral oxide supports as described for example in EP-A- 293815, or in US-A-5262498, or in US-A-5688880, or in US-A-5854362, or in US-A- 5399636 or in H. G. Alt, P. Schertl, A. Koppl, "Polymerization of ethylene with metallocene/methylaluminoxane catalysts supported on polysiloxane microgels and silica.” in J. Organometal. Chem., 568, 263-269, 1998, or in M. Galan-Fereres, T. Koch, E. Hey-Hawkins, M.S.
  • the strong Lewis acid moieties B(Arp) 3 (A ⁇ F being perfluorinated aromatic nucleus) were covalently anchored on silica surface by their silanol.
  • Work on the possible anchorage of perfluorinated boranes on different support such as for example polystyrene or silica was reported in US-A- 5 427 991 or in US-A-5 869 723 or in EP-A-1 359166 or in WO 03/035708.
  • the counter cations of the grafted perfluorinated borate were derivatives of anilinium or trityl cations.
  • Kaneko et al. have anchored the p-trimethoxysilyl-(N,N-dimethylanilinium) on a silica surface to afford an activating support for olefin polymerisation by addition of lithien tetrakis(pentafluorophenyl)borate. They also claim the use of dimethyldimethoxysilane as co-grafting agent.
  • the present invention discloses an activating support for activating metallocene or post-metallocene catalyst components in the homo- or co- polymerisation of ethylene and alpha-olefins characterised in that the activating species is provided either by a pair phosphonium-borate or by a pair phosphonium- aluminate in the presence of a Bronsted acid, said pair being anchored on a silica support.
  • the present invention also discloses a method for preparing an activating support that comprises the steps of: a) reacting phosphine R 3 P with a borane or an alane in order to provide a classical phosphino-borane or a phosphino-alane pair, wherein each R is independently selected from hydrogen or from substituted or unsubstituted aryl or alkyl having at most 10 carbon atoms, with the restriction that they are not all hydrogen in order to provide steric hindrance, or from Si(RO)3- n R"n group wherein R 1 and R" are independently selected from alkyl having from 1 to 8 carbon atoms and n is 0, 1 , 2 or 3; b) optionally reacting the reaction product of step a) with a strong Bronsted acid HX wherein X is triflate (OTf) or halogen or OSi — SiO 2 or OS(O 2 ) -RF - OSi-
  • one R is Si(R'O) 3 . n R"n group, said group being preferably used to also anchor the phosphonium part on the silica surface. This method is represented in Scheme 1'.
  • the support is silica.
  • the support may be modified in order to tailor its acidity, its specific surface, its pore volume, and its hydrophobic or hydrophilic properties.
  • the supports are modified by addition of aluminium alkyl, preferably AIMe 3 , to create additional Lewis acid sites or Bronsted acid sites highly suitable for the activation of metallocene components.
  • the silica support Prior to being suspended in the apolar solvent of step c), the silica support may be functionalised with a perfluorinated alkylsulfonic acid chain selected from SiO 2 - ORFSO 3 H or from SiO 2 -R 11 FSO 3 H whererin R F is
  • Perfluoroalkanesulfonic acid-containing solids generally called "Nafion"type- functionalised silica, have been previously reported by Harmer et al. in M.A. Harmer, Q. Sun, M.J. Michalczyk, Z. Yang, in Chem. Commun., 1997, 1803-1804; or in D.J. Macquarrie, S.J. Taverner, M.A.
  • step b) is present and a strong Bronsted acid HX is added.
  • at least one R is Si(RO) 3 . n R"n group, said group being preferably used to also anchor the phosphonium part on the silica surface.
  • the strong Bronsted acid is additionally used to create a zwitterionic pair phosphonium borate R 3 P + H, X " BR 1 3 or phosphonium aluminate R 3 P + H, X " AIR 1 3 . This is represented in Scheme 2.
  • Ar F is a perfluorinated aryl group.
  • the activating center may be prepared following the scheme herebelow, prior to being anchored onto the support,
  • X is triflate (OTf), chlorine, OSiJ - SiO 2 or OS(O 2 ) -RF - OSi-J -SiO 2 , or
  • R 3 P is preferably reacted with a borane.
  • a borane Among the preferred boranes one can cite B(C 6 F 5 ) 3 . Without wishing to be bound by a theory, it is believed that if phosphine is placed directly on the silica it is oxidised. It is protected by complexation with borane without being bound too strongly.
  • R are independently selected from hydrogen, methyl, isopropyl, tert-butyl, substituted or unsubstituted phenyl group with the restriction that not all R are hydrogen Si(R'O)3 -n R"n-
  • at least one R is as bulky as or bulkier than isopropyl.
  • two R are substituted or unsubstituted phenyl groups and the third R is Si(R'O) 3-n R"n, providing a chain for anchorage.
  • the present invention also discloses the double anchorage of zwitterionic system performed by covalently anchoring both the borate or alane anion and the phosponium cation on a support.
  • the support carrying phosphonium complexes is passivated by addition of a non-nucleophile trimethylsilylating agent of formula
  • the amount of trimethylsilylating agent is selected to provide at least 5 equivalents of silanol with respect to silanol present in the starting silica-based support.
  • Late transition metal complexes of the present invention preferably include ⁇ -diimine Ni complexes as disclosed by Brookhart in WO96/ 23010 or bis(imino)pyridyl Iron(ll) or Cobalt(ll) complexes as disclosed by Bristovsek et al. (GJ. P. Bristovsek, V.C. Gibson, B.S. Kimberley, P.J.
  • the activating supports of the present invention are used with metallocene catalyst components, said components are preferably dialkylated, more preferably dimethylated. Dialkylation can be produced in situ by an alkylating agent such as aluminium alkyl.
  • the present invention thus discloses a method for oligomerising or for homo- or co- pelimerising ethylene or alpha-olefins that comprises the steps of: a) providing an activating support as described in any one of the embodiments hereabove; b) impregnating a dialkylated metallocene or a post-metallocene catalyst component onto the activating support. c) optionally adding a scavenger; d) injecting the monomer and optional comonomers simultaneously with or after the catalyst system; e) maintaining under polymerisation conditions; f) retrieving an oligomer or a polymer.
  • the scavenger is typically selected from aluminum alkyl. Preferably it is triethylaluminium (TEAL) or triisobutylaluminium (TIBAL). It is preferable to use a scavenger.
  • TEAL triethylaluminium
  • TIBAL triisobutylaluminium
  • the monomer is preferably ethylene or propylene.
  • the comonomer is preferably ethylene, propylene or 1-hexene.
  • Phosphonium/borates or phosphonium/alanes were used to prepare anion-cation pairs.
  • AIMe 3 were then added dropwise. The reaction was exothermal and the solution was kept under stirring at room temperature for a period of time of 1 hour. 300 ⁇ L of water were added to the suspension that was kept at room temperature for a period of time of 3 hours. It was then heated at a temperature of 100 0 C for a period of time of 16 hours.
  • the solution of phosphonium borate was added dropwise to the support suspension and it was kept under mixing for 1 hour at room temperature (about 25 0 C) and then it was heated at a temperature of 80 °C for 12 hours and at a temperature of 100 0 C for
  • This sample was prepared by reacting triethoxyethyldiphenylphosphine, borane and an heterogeneous support (S2) (1 ,2,2-thfluoro-1-trifluoromethyl-ethane sulfonic acid- containing silica gel).
  • S2 heterogeneous support
  • reaction mixture was heated at a temperature of 80 0 C during 12h then at a temperature of 100 0 C during 3h more. After cooling, the solid was filtered and washed under argon with dry toluene (30 ml_, 2 times), then with pentane (20 ml_) then evacuated under vacuum 4h.
  • the perfluorosulfonic acid loading determined by thermogravimetry is 0.54 mmol.g '1 .
  • reaction of phosphino borane with support (S2) the obtained support S2 was activated under vaccum at 80°C for 6 hours. Then, 30 mL of distilled toluene were added. The solution was stirred for 30 mn.
  • sample A4 only the cationic part was anchored on the silica support and the anionic part was free. In sample A'4, both cationic and anionic parts were anchored on the support.
  • Metallocene catalyst component a fresh solution of the dimethylated catalyst system sold by Total Petrochemicals under the name Z12Hsm.
  • Activating support 10 mg of activating support.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Molecular Biology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)

Abstract

L'invention porte sur l'ancrage covalent d'anions non coordinants sur des supports minéraux en vue de la préparation de supports d'activation pour la polymérisation d'éthylène et d'alpha-oléfines, l'espèce d'activation étant formée par une paire phosphonium-borate ou phosphonium-alane. L'invention porte également sur l'ancrage covalent concomitant de systèmes zwittérioniques contenant à la fois les parties anions non coordinants et contre-cations des supports d'activation.
EP08860188A 2007-12-11 2008-12-11 Activation de supports basés sur des complexes de phosphonium Withdrawn EP2220129A2 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP08860188A EP2220129A2 (fr) 2007-12-11 2008-12-11 Activation de supports basés sur des complexes de phosphonium

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP07291495A EP2070953A1 (fr) 2007-12-11 2007-12-11 Activation de supports basés sur des complexes de phosphonium
PCT/EP2008/010521 WO2009074316A2 (fr) 2007-12-11 2008-12-11 Supports d'activation à base de complexes de phosphonium
EP08860188A EP2220129A2 (fr) 2007-12-11 2008-12-11 Activation de supports basés sur des complexes de phosphonium

Publications (1)

Publication Number Publication Date
EP2220129A2 true EP2220129A2 (fr) 2010-08-25

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Country Status (3)

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US (1) US8338324B2 (fr)
EP (2) EP2070953A1 (fr)
WO (1) WO2009074316A2 (fr)

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Also Published As

Publication number Publication date
WO2009074316A2 (fr) 2009-06-18
EP2070953A1 (fr) 2009-06-17
US8338324B2 (en) 2012-12-25
WO2009074316A3 (fr) 2009-11-19
US20110184133A1 (en) 2011-07-28
WO2009074316A4 (fr) 2010-01-14

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